CN108199083A - Electrolyte of sodium-ion battery and preparation method thereof, sodium-ion battery - Google Patents
Electrolyte of sodium-ion battery and preparation method thereof, sodium-ion battery Download PDFInfo
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- CN108199083A CN108199083A CN201810019950.7A CN201810019950A CN108199083A CN 108199083 A CN108199083 A CN 108199083A CN 201810019950 A CN201810019950 A CN 201810019950A CN 108199083 A CN108199083 A CN 108199083A
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- sodium
- electrolyte
- ion battery
- solvent
- carbonate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of electrolyte of sodium-ion battery, and according to mass percent meter, the electrolyte includes following components：Electrolyte solvent is 30~75%, sodium salt is 7~15%, polymer is 8~12% and ceramic powder is 5~55%.The present invention also provides a kind of methods of sodium-ion battery and the electrolyte for preparing sodium-ion battery.The present invention can improve the security performance and cycle performance of sodium ion electronics, and improve the interfacial contact between electrolyte and electrode.
Description
Technical field
The present invention relates to sodium-ion battery fields, and in particular to a kind of electrolyte of sodium-ion battery and preparation method thereof,
Sodium-ion battery.
Background technology
Lithium ion battery is in the portable electronic products such as mobile phone, laptop and electric tool, electric bicycle, electricity
Being widely used in electrical automobile greatly changes people’s lives custom, the mode of production.Because it is close with voltage height, energy
It spends the advantages that high, energy efficiency is high and has irreplaceable role.It is swift and violent with electric vehicle and extensive energy storage demand
Increase, the consumption of lithium can be increased and continuously and healthily.However, abundance of the elemental lithium in the earth's crust is very low, and distribution on global
It is extremely uneven, by the serious development for restricting electric vehicle and extensive energy storage.
There is content relative abundance of the sodium in the earth's crust of similar physico-chemical property and widely distributed with lithium, it may have with
The similar deintercalation mechanism of lithium can realize the Reversible Cycle in electrode material, and the theoretical specific capacity of metallic sodium is 1166mAh/
G although lower than lithium ion battery, can replace the certain applications scene of lithium ion battery, such as to energy density require compared with
Low large-scale energy storage system, therefore the research and development of sodium ion secondary battery are expected to alleviate lithium resource shortage to a certain extent
And the problem of bringing.
But sodium is different from the activity of lithium, applicable elements can be different.Sodium-ion battery under current room temperature has and makes
Organic system with organic electrolyte and the aqueous systems using aqueous solution electrolysis liquid.The general electrode range of aqueous electrolyte it is relatively low and
With relatively low energy density, and water system cannot make cathode using metallic sodium；And for organic system electrolyte, due to gold
Category sodium is very active, and side reaction can occur with it for current organic solvent, meanwhile, then there are volatile, flammable etc. latent for organic system
In safety factor.In addition, organic system and aqueous electrolyte all deposit sodium ion leads to dendritic growth in negative terminal surface nonuniform deposition,
Initiation battery short circuit, further there may be the safety problems such as burning, explosion.
The problems such as dendrite, combustion explosion can be alleviated using solid-state sodium ion conductor electrolyte.However, all-solid sodium ion
Interfacial contact is very poor between conductor electrolyte and electrode.Moreover, during charge and discharge cycles, it can be because of the volume of electrode repeatedly
Change and make interfacial contact worse and worse, lead to the attenuation of battery performance.
Invention content
In consideration of it, it is necessary to provide a kind of electrolyte of sodium-ion battery, the security performance of sodium ion electronics can be improved
And cycle performance, and improve the interfacial contact between electrolyte and electrode, the present invention also provides a kind of sodium-ion battery and
A kind of method for preparing the electrolyte.
First aspect present invention provides a kind of electrolyte of sodium-ion battery, according to mass percent meter, the electrolyte
Including following components：Electrolyte solvent is 30~75%, sodium salt is 7~15%, polymer is 8~12% and ceramic powder is
5~55%.
In a preferred embodiment, the electrolyte solvent includes at least one of following：Carbonate-based solvent
And ether solvent.
In a preferred embodiment, the carbonate-based solvent includes at least one of following：Vinyl carbonate,
Propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate.
In a preferred embodiment, the ether solvent includes at least one of following：Tetrahydrofuran, 2- methyl
Tetrahydrofuran, 1,3- dioxolanes, glycol dimethyl ether, dimethoxymethane, 1,2- dimethoxies, diethylene glycol dimethyl ether,
Diethoxyethane.
In a preferred embodiment, the sodium salt includes at least one of following：Sodium perchlorate, double trifluoro sulphonyl
At least one of imines sodium, sodium hexafluoro phosphate, bis- (fluorine sulphonyl) amine sodium.
In a preferred embodiment, the polymer includes at least one of following：Polyethylene oxide, poly- methyl
Methyl acrylate, polyacrylonitrile, Kynoar, Kynoar-hexafluoropropene.
In a preferred embodiment, ceramic powder includes at least one of following：SiO2、β″-Al2O3, sodium surpass from
Sub- conductor, sulfenyl sodium ion conductor.
In a preferred embodiment, the sodium superionic conductors includes at least one of following：NaZr2P3O12、
Na4Zr2Si3O12, the sulfenyl sodium ion conductor includes at least one of following：Na3PS4、Na3SbS4、Na10SnP2S12。
Second aspect of the present invention provides a kind of sodium-ion battery, the sodium-ion battery include cathode, anode and with institute
Cathode and the electrolyte of anode contact are stated, the electrolyte is the electrolyte of the sodium-ion battery.
Third aspect present invention provides a kind of method for the electrolyte for preparing sodium-ion battery, the method includes：20
Within the temperature range of~150 DEG C and in dry atmosphere, according to mass percent meter, by electrolyte solvent for 30~
75%th, sodium salt is 7~15%, polymer is 8~12% and ceramic powder be 5~55% be uniformly mixed obtain the sodium from
The electrolyte of sub- battery.
A kind of electrolyte of sodium-ion battery provided by the invention, for solid-state or semisolid, polymer and ceramic powder
Introducing can widen electrolyte electrochemical window, expand the range of choice of positive electrode, for example using high-voltage anode, carry
The energy density of high battery；The liquid electrolyte that electrolyte solvent after dissolving sodium salt is formed enough is reduced with ceramic powder to be polymerize
The glass transition temperature of object can improve ionic conductivity, and electrolyte is allowed also to have higher ionic conductance at lower temperatures
Rate assigns the ability of battery more wide operating temperature range, in addition, the addition of ceramic powder and polymer can also reduce electrolyte
The content or ratio of middle liquid electrolyte increase safety, in addition, ceramic powder is introduced with polymer, can increase electrolyte
Compatibility between sodium can form stable electrode electrolyte interface film, therefore can be by the use of metallic sodium as negative
Pole can significantly improve battery energy density.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail, it should be noted that following embodiment be for
It is convenient to technical staff and understands the present invention, and do not lie in and limit the scope of the invention, those of ordinary skill in the art,
Under the premise of the basic conception for not departing from the present invention, the improvement made should belong to the scope of protection of the present invention.
The present invention provides a kind of electrolyte for the sodium-ion battery that can be rendered as solid-state or semisolid, according to quality
Percentages, the electrolyte can include following components：Electrolyte solvent is 30~75%, sodium salt is 7~15%, polymer
It is 5~55% for 8~12% and ceramic powder.Wherein, electrolyte solvent is preferably：Carbonate-based solvent and ether solvent
Deng, wherein, carbonate-based solvent is preferably vinyl carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid first
Ethyl ester, ether solvent are preferably tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, glycol dimethyl ether, dimethoxy
Methane, 1,2- dimethoxies, diethylene glycol dimethyl ether, diethoxyethane.Sodium salt is preferably：Sodium perchlorate, double trifluoro sulphonyl
Imines sodium, sodium hexafluoro phosphate, bis- (fluorine sulphonyl) amine sodium.Polymer is preferably：Polyethylene oxide, is gathered polymethyl methacrylate
Acrylonitrile, Kynoar, Kynoar-hexafluoropropene.Ceramic powder is preferably：SiO2, β "-Al2O3, sodium super-ionic lead
Body, sulfenyl sodium ion conductor；Wherein sodium superionic conductors is preferably NaZr2P3O12、Na4Zr2Si3O12, sulfenyl sodium ion conductor is excellent
It is selected as：Na3PS4、Na3SbS4、Na10SnP2S12。
Polymer, ceramic powder and the sodium salt of the present invention, solvent interaction, widen electrolyte electrochemical stability window
Mouthful, electrolyte that is uniform, stablizing can be obtained；And ceramic powder and liquid electrolyte enough reduce the gamma transition of polymer
Temperature conducive to transporting for sodium ion, improves ionic conductivity, and electrolyte is allowed also to there is higher ion to transport at lower temperatures
Movement Capabilities in addition, ceramic powder can also reduce the liquid electrolyte liquid hold-up dissolved with sodium salt with polymer, increase safety.
In addition, the addition of ceramic powder and polymer, with the compatibility between electrolyte and sodium or can form stable electricity
Pole-electrolyte interface film, therefore can significantly improve battery energy density by the use of sodium as cathode.
Since the organic solvent in electrolyte has the characteristics that volatile, inflammable, toxic, the polymer of addition can be by liquid
State electrolyte is coated in its skeleton, can be reduced the volatilization, leakage, the possibility burnt of solvent, be reduced security risk, inhibit
Dendritic growth.Due to containing a certain amount of liquid electrolyte in the electrolyte of the sodium-ion battery of the present invention, conductivity is not low
In the conductivity of liquid electrolyte, also can easily impregnating porous electrode, existing solid-state sodium ion conductor electricity can be improved
The problem of interfacial contact is poor between matter and electrode is solved, contact impedance is small.
The electrolyte of sodium-ion battery provided by the invention, be solid-state or semisolid, can have both existing solid-state sodium from
The advantages of sub- conductor electrolyte and overcome its there are the shortcomings that, it is good with the electrode material matching of high-energy density, reduce interface
Impedance, effectively promotes the energy density and chemical property of sodium-ion battery, but also improves the safety of sodium-ion battery
Energy.
The specific embodiment of the electrolyte of sodium-ion battery of the present invention and preparation method thereof is provided below.
Embodiment 1：
The electrolyte of a kind of sodium-ion battery that the present embodiment is provided, in parts by weight, the electrolysis including 30wt%
Matter solvent, the sodium salt of 15wt%, 12wt% polymer and 43wt% ceramic powder.
Preparation method is as follows：In temperature is kept to be 20 DEG C of dry environment, in the electrolyte solvent of 30wt% successively
The ceramic powder of the sodium salt of 15wt%, 12wt% polymer and 43wt% are added in, and is sufficiently stirred during addition and makes it
It is uniformly mixed to get to the electrolyte of sodium-ion battery.
Embodiment 2：
The electrolyte of a kind of sodium-ion battery that the present embodiment is provided, in parts by weight, the electrolysis including 30wt%
Matter solvent, the sodium salt of 7wt%, 8wt% polymer and 55wt% ceramic powder.
Preparation method is as follows：In temperature is kept to be 20 DEG C of dry environment, in the electrolyte solvent of 30wt% successively
The ceramic powder of the sodium salt of 7wt%, 8wt% polymer and 55wt% are added in, and being sufficiently stirred during addition makes it mixed
It closes uniformly to get to the electrolyte of sodium-ion battery.
Embodiment 3：
The electrolyte of a kind of sodium-ion battery that the present embodiment is provided, in parts by weight, the electrolysis including 65wt%
Matter solvent, the sodium salt of 15wt%, 12wt% polymer and 8wt% ceramic powder.
Preparation method is as follows：In temperature is kept to be 20 DEG C of dry environment, in the electrolyte solvent of 65wt% successively
Sodium salt, the polymer of 12wt% and the ceramic powder of 8wt% of 15wt% are added in, and is sufficiently stirred during addition and makes it
It is uniformly mixed to get to the electrolyte of sodium-ion battery.
Embodiment 4：
The electrolyte of a kind of sodium-ion battery that the present embodiment is provided, in parts by weight, the electrolysis including 75wt%
Matter solvent, the sodium salt of 7wt%, the polymer of 10wt% and 8wt% ceramic powder.
Preparation method is as follows：In temperature is kept to be 80 DEG C of dry environment, in the electrolyte solvent of 75wt% successively
Sodium salt, the polymer of 10wt% and the ceramic powder of 8wt% of 7wt% are added in, and is sufficiently stirred during addition and makes it
It is uniformly mixed to get to the electrolyte of sodium-ion battery.
Embodiment 5：
The electrolyte of a kind of sodium-ion battery that the present embodiment is provided, in parts by weight, the electrolysis including 72wt%
Matter solvent, the sodium salt of 12wt%, the polymer of 8wt% and 8wt% ceramic powder.
Preparation method is as follows：In temperature is kept to be 150 DEG C of dry environment, in the electrolyte solvent of 72wt% successively
Sodium salt, the polymer of 8wt% and the ceramic powder of 8wt% of 12wt% are added in, and is sufficiently stirred during addition and makes it
It is uniformly mixed to get to the electrolyte of sodium-ion battery.
The electrolyte of sodium-ion battery obtained by embodiment 1-5, ceramic powder accounting increase, the electrolysis of sodium-ion battery
Matter form can become solid-state from semisolid, and the electrolyte of solid-state or semisolid has broader electrochemical stability window, can be with height
The electrode material cooperation of energy density, can significantly improve battery energy density；With higher ionic conductivity, battery have compared with
High high rate performance；Since it reduces the content of liquid electrolyte, thus the safety of battery can also be increased；Further, since
Containing a certain amount of liquid electrolyte, good between electrode contacts；Polymer and ceramics can also improve electrolyte with
Compatibility between metallic sodium can use metallic sodium to further improve the energy density of battery, and polymer is also as cathode
It is flexible to assign electrolyte, can be used for flexible battery.
One embodiment of the present invention provides a kind of sodium-ion battery, including appointing in cathode and anode and embodiment 1-5
The electrolyte of one embodiment, wherein, cathode may be used the electrode material with high-energy density such as sodium metal and be made, and anode can
To be made of high voltage material, electrolyte is good with the interfacial contact of cathode and anode, sodium-ion battery obtained, has higher
Battery energy density, while there is higher safety.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although reference
The present invention is described in detail in preferred embodiment, it will be understood by those of ordinary skill in the art that, it can be to the present invention's
Technical solution is modified or equivalent replacement, without departing from the spirit and scope of technical solution of the present invention.
Claims (10)
1. a kind of electrolyte of sodium-ion battery, which is characterized in that according to mass percent meter, the electrolyte is included with the following group
Point：Electrolyte solvent is 30~75%, sodium salt is 7~15%, polymer is 8~12% and ceramic powder is 5~55%.
2. the electrolyte of sodium-ion battery according to claim 1, which is characterized in that the electrolyte solvent includes following
At least one of：Carbonate-based solvent and ether solvent.
3. the electrolyte of sodium-ion battery according to claim 2, which is characterized in that the carbonate-based solvent include with
It is at least one of lower：Vinyl carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate.
4. the electrolyte of sodium-ion battery according to claim 2, which is characterized in that the ether solvent include it is following in
It is at least one：Tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, glycol dimethyl ether, dimethoxymethane, 1,2-
Dimethoxy, diethylene glycol dimethyl ether, diethoxyethane.
5. the electrolyte of sodium-ion battery according to claim 1, which is characterized in that the sodium salt include it is following at least
It is a kind of：At least one of sodium perchlorate, double trifluorosulfonimide sodium, sodium hexafluoro phosphate, bis- (fluorine sulphonyl) amine sodium.
6. the electrolyte of sodium-ion battery according to claim 1, which is characterized in that the polymer include it is following in extremely
Few one kind：Polyethylene oxide, polymethyl methacrylate, polyacrylonitrile, Kynoar, Kynoar-hexafluoropropene.
7. the electrolyte of sodium-ion battery according to claim 1, which is characterized in that ceramic powder include it is following at least
It is a kind of：SiO2、β″-Al2O3, sodium superionic conductors, sulfenyl sodium ion conductor.
8. the electrolyte of sodium-ion battery according to claim 7, which is characterized in that the sodium superionic conductors include with
It is at least one of lower：NaZr2P3O12、Na4Zr2Si3O12, the sulfenyl sodium ion conductor includes at least one of following：Na3PS4、
Na3SbS4、Na10SnP2S12。
9. a kind of sodium-ion battery, which is characterized in that the sodium-ion battery include cathode, anode and with the cathode and institute
The electrolyte of anode contact is stated, the electrolyte is the electrolyte of claim 1-8 any one of them sodium-ion batteries.
A kind of 10. method for the electrolyte for preparing sodium-ion battery, which is characterized in that the method includes：At 20~150 DEG C
By electrolyte solvent it is 30~75% according to mass percent meter, sodium salt 7 in temperature range and in dry atmosphere
~15%, polymer is 8~12% and ceramic powder is 5~55% uniformly mixed electrolysis for obtaining the sodium-ion battery
Matter.
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| CN201810019950.7A CN108199083A (en) | 2018-01-09 | 2018-01-09 | Electrolyte of sodium-ion battery and preparation method thereof, sodium-ion battery |
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| CN201810019950.7A CN108199083A (en) | 2018-01-09 | 2018-01-09 | Electrolyte of sodium-ion battery and preparation method thereof, sodium-ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786812A (en) * | 2019-01-15 | 2019-05-21 | 北京理工大学 | A kind of photo-cured solid composite electrolyte and preparation method thereof |
| CN110649314A (en) * | 2019-09-24 | 2020-01-03 | 广东天劲新能源科技股份有限公司 | All-solid-state sodium-sulfur battery and preparation method thereof |
| CN111987356A (en) * | 2020-08-31 | 2020-11-24 | 上海空间电源研究所 | Long-term circulating sodium-carbon fluoride secondary battery and preparation method thereof |
| CN113964376A (en) * | 2021-10-18 | 2022-01-21 | 南京大学 | Preparation and application of novel low eutectic agent |
| CN114613946A (en) * | 2022-04-07 | 2022-06-10 | 深圳市寒暑科技新能源有限公司 | Manufacturing method of electrode pole piece of sodium-ion battery and semisolid sodium-ion battery |
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| CN102195087A (en) * | 2010-03-02 | 2011-09-21 | 索尼公司 | Nonaqueous electrolyte composition and nonaqueous electrolyte battery |
| CN103038924A (en) * | 2010-06-17 | 2013-04-10 | 国立科学研究中心 | Method for producing a lithium or sodium battery |
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| CN109786812A (en) * | 2019-01-15 | 2019-05-21 | 北京理工大学 | A kind of photo-cured solid composite electrolyte and preparation method thereof |
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| CN113964376A (en) * | 2021-10-18 | 2022-01-21 | 南京大学 | Preparation and application of novel low eutectic agent |
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